Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
  • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
  • C07D471/06—Peri-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
  • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
  • C07D221/04—Ortho- or peri-condensed ring systems
  • C07D221/18—Ring systems of four or more rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
  • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series

Definitions

• the present invention relates to perylene imide monocarboxylic acids of the general formula ##STR2## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are identical or different and are hydrogen, or one to nine radicals are a radical selected from the group consisting of an unsubstituted or substituted carbocyclic aromatic radical, an unsubstituted or substituted heterocyclic aromatic radical, halogen, unsubstituted or substituted C 1 -C 18 alkyl, --OR 10 , --CN, --NR 11 R 12 , --COR 13 ,
• R 13 is C 1 -C 18 alkyl, C 6 -C 10 aryl, or benzyl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or a five- to seven-membered heterocyclic radical
• R 11 and R 12 are each independently of the other hydrogen; C 1 -C 18 alkyl, C 3 - to C 24 cycloalkyl, C 6 -C 10 aryl or 5- to 7-membered heteroaryl, each of which is unsubstituted or substituted by cyano groups or hydroxy groups, or wherein R 11 and R 12 , together with at least one of the other radicals R 2 to R 9 , are a 5- or 6-membered carbocyclic or heterocyclic ring,
• R 10 is hydrogen, C 1 -C 18 alkyl, C 3 - to C 24 cycloalkyl, C 6 -C 10 aryl or 5- to 7-membered heteroaryl,
• R 14 is hydrogen; C 1 -C 18 alkyl, C 3 - to C 24 cycloalkyl, C 1 -C 4 alkylaryl, each of which i unsubstituted or substituted by cyano groups, hydroxy groups or C 1 -C 4 alkoxycarbonyl groups; C 6 -C 10 aryl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl groups or C 1 -C 4 alkoxy groups, or a 5- to 7-membered heterocycle,
• R 15 is the radical of a coupling component, or C 6 -C 10 aryl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl groups or C 1 -C 4 alkoxy groups, and
• X is C 1 -C 37 alkanediyl, C 2 -C 37 alkenediyl, C 2 -C 37 alkynediyl, C 5 -C 12 cycloalkylene, C 5 -C 12 cycloalknylene, C 5 -C 12 cycloalkynylene, a divalent carbocyclic or heterocyclic aromatic radical.
• This invention also relates to perylene-3,4-dicarboxylic acid imides of the general formula II ##STR3## wherein R 16 has the same meaning as R 1 to R 9 and, within the scope of the definition, may be identical to or different from those radicals, as well as to a process for the preparation of the compounds I and II and to their use as colourants.
• Perylene-3,4:9,10-tetracarboxylic acid bisimides have been found useful as lightfast colourants.
• their use as highly stable fluorescent colourants was opened up by the introduction of solubility-increasing groups (see e.g. EP-A 39085). Owing to their good properties, these colourants are particularly interesting as fluorescent markers, in which case, however, the use of monofunctionalised colourants is required.
• the use of said colourants in homogeneous solution is substantially restricted to non-aqueous media.
• perylene imide derivatives which are monofunctionalised and which are also soluble in aqueous media.
• perylene imide monocarboxylic acids are to be provided.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are identical or different and are hydrogen, or one to nine radicals are a radical selected from the group consisting of an unsubstituted or substituted carbocyclic aromatic radical, an unsubstituted or substituted heterocyclic aromatic radical, halogen, unsubstituted or substituted C 1 -C 18 alkyl, --OR 10 , --CN, --NR 11 R 12 , --COR 13 , --NR 14 COR 13 , --NR 10 COOR 13 , --NR 10 CONR 11 R 12 , --NHSO 2 R 13 , --SO 2 R 13 , --SOR 13 , --SO 2 OR 13 , --CONR 11 R 12 , --SO 2 NR 11 R 12 , --N ⁇ NR 15 , --OCOR 13 and --OCONHR 13 , wherein pairs of adjacent radicals can form a carbocyclic or heterocyclic ring, wherein pairs of adjacent
• the unsubstituted or substituted carbocyclic aromatic radical may preferably be mono- to tetracyclic, particularly preferably mono- and bicyclic, radicals containing five to seven carbon atoms per ring, for example phenyl, diphenyl and naphthyl.
• the unsubstituted or substituted heterocyclic aromatic radical may preferably be a mono- to tricyclic radical which preferably contains five to seven ring atoms.
• This radical may consist just of at least one heterocyclic ring, or the heterocyclic ring or rings may contain at least one fused benzene ring.
• pyridyl pyrimidyl
• pyrazinyl triazinyl
• furanyl pyrrolyl
• thiophenyl quinolyl
• isoquinolyl coumarinyl
• benzofuranyl benzimidazolyl
• benzoxazolyl dibenzfuranyl
• benzothiophenyl dibenzothiophenyl
• indolyl carbazolyl
• pyrazolyl imidazolyl
• oxazolyl isoxazolyl
• thiazolyl indazolyl
• benzothiazolyl pyridazinyl, cinnolyl, quinazolyl, quinoxalyl, phthalazinyl, phthalazindionyl, phthalimidyl, chromonyl, naphtholactamyl, benzopyridonyl, ortho-sulfobenzimidyl, maleinimidyl, male
• the carbocyclic and/or heterocyclic aromatic radicals are mono- or poly-substituted by customary substituents, particularly preferably by substituents which do not bring about water-sulubility. Examples to be mentioned are:
• halogen typically fluoro, chloro, bromo and iodo, preferably chloro
• C 1 -C 18 alkyl for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, preferably C 1 -C 12 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl
• R 13 is C 1 -C 18 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, preferably C 1 -C 12 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-
• R 11 and R 12 are hydrogen; C 1 -C 18 alkyl which is unsubstituted or cyano group- or hydroxyl group-substituted as mentioned above, preferably C 1 -C 12 alkyl, particularly preferably C 1 -C 8 alkyl, very particularly preferably C 1 -C 4 alkyl, as mentioned above, C 3 - to C 24 cycloalkyl, preferably C 5 -, C 6 -, C 12 -, C 15 -, C 16 -, C 20 - and C 24 cycloalkyl, aryl or heteroaryl, preferably derived from the above-mentioned carbo- and heterocyclic aromatic radicals, in particular phenyl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or wherein R 11 and R 12 , together with at least one of the other radicals R 2 to R 9 , form a 5- to 6-membered
• the substituents at the alkyl groups are mono- or dialkylated amino groups, aryl radicals, for example naphthyl or, preferably, phenyl which is unsubstituted or substituted by halogen, alkyl or --O-alkyl, or also heterocyclic aromatic radicals, such as 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinolyl or 1-, 3-, 4-, 6-, or 8-isoquinolyl radicals.
• aryl radicals for example naphthyl or, preferably, phenyl which is unsubstituted or substituted by halogen, alkyl or --O-alkyl, or also heterocyclic aromatic radicals, such as 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 6-benz
• this alkyl can be branched or unbranched and preferably contains 1 to 18, in particular 1 to 12, more preferably 1 to 8 and, particularly preferably, 1 to 4, carbon atoms.
• Typical examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl
• R 10 is hydrogen, C 1 -C 18 alkyl as defined for R 13 , including the preferred variants cited there, C 3 - to C 24 cycloalkyl, preferably C 5 , C 6 -, C 12 -, C 15 -, C 16 -, C 20 - and C 24 -cycloalkyl, C 6 -C 10 aryl, such as naphthyl and phenyl, preferably unsubstituted phenyl and phenyl which is substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or 5- to 7-membered heteroaryl.
• R 10 examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl
• R 11 and R 12 have the meanings mentioned above.
• preferred radicals to be mentioned are: amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, 2-hydroxyethylamino, 2-hydroxypropylamino, N,N-bis(2-hydroxyethyl)amino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicosanylamino, cyclotetracosanylamino, phenylamino, N-methylphenylamino, benzylamino, dibenzylamino, piperidyl or morpholyl;
• R 13 has the meaning cited above.
• R 13 to be mentioned are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, tert-butyl, tertamyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl (corresponding to 1-ethyl-n-propyl), 4-heptyl (corresponding to 1-n-propyl-1-n-butyl), 5-nonyl (or: 1-n-butyl-n-pentyl), 6-undecyl (or: 1-ethyl-n-butyl), 7-tridecy
• R 13 has the meaning given above, and R 14 is hydrogen; C 1 -C 18 alkyl, C 3 - to C 24 cycloalkyl, C 1 -C 4 alkylaryl, each of which is unsubstituted or substituted by cyano groups, hydroxyl groups or C 1 -C 4 alkoxycarbonyl groups; C 6 -C 10 aryl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl groups or by C 1 -C 4 alkoxy groups, or a 5- to 7-membered heterocycle, the meaning of the individual radicals, such as alkyl, alkoxy, aryl etc., conforming to the above definitions thereof, including the preferred ranges cited there.
• radicals to be mentioned are: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N-(4-amino)-phthalimido;
• R 13 has the meaning given above.
• radicals to be mentioned are: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino;
• R 13 has the meaning given above.
• radicals to be mentioned are: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl;
• R 13 has the meaning cited above. Radicals to be mentioned as examples are phenylsulfoxidyl and methylsulfoxidyl;
• R 13 has the meaning given above.
• R 13 to be mentioned are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl;
• R 11 and R 12 have the meanings given above.
• radicals to be mentioned are: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperidylcarbamoyl;
• radicals to be mentioned are: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl;
• R 15 is the radical of a coupling component or a phenyl radical which is unsubstituted or substituted by halogen, alkyl or --O-alkyl, where halogen and alkyl have the meanings given above.
• Alkyl in the definitions of R 15 can contain one of the preferred numbers of carbon atoms indicated above. Examples of R 15 to be mentioned are: the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or p-N,N-dimethylaminophenyl radicals.
• R 13 has the meaning cited above.
• R 1 3 to be mentioned are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl;
• R 13 has the meaning cited above.
• R 13 to be mentioned are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
• Halogen may be fluoro, chloro, bromo and iodo. Fluoro and chloro are preferred.
• Unsubstituted or substituted C 1 -C 18 alkyl can be: methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, preferably C 1 -C 12 alkyl, such as methyl, ethyl, n-propyl, iso
• R 18 is C 1 -C 18 alkyl, typically methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undec
• the substituents at the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, preferably, phenyl which is unsubstituted or substituted by halogen, alkyl or --O-alkyl, or also heterocyclic aromatic radicals, such as the 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinolyl or 1-, 3-, 4-, 6-, or 8-isoquinolyl radicals.
• aryl radicals such as naphthyl or, preferably, phenyl which is unsubstituted or substituted by halogen, alkyl or --O-alkyl, or also heterocyclic aromatic radicals, such as the 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl,
• this alkyl can be branched or unbranched and preferably contains 1 to 18, in particular 1 to 12, more preferably 1 to 8 and, particularly preferably, 1 to 4, carbon atoms.
• Typical examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tertbutyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl,
• R 10 in --OR 10 can be: hydrogen, C 1 -C 18 alkyl as defined above for R 13 , including the preferred variants mentioned there.
• preferred radicals R 10 to be mentioned are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, tri
• Examples of preferred --OR 10 radicals are: hydroxy, methoxy, --O-ethyl, --O-i-propyl-, --O-i-butyl, --O-phenyl, --O-2,5-di-tertbutylphenyl.
• R 11 and R 12 in --NR 11 R 12 can be the radicals defined above.
• Typical examples of preferred radicals are: amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, 2-hydroxyethylamino, 2-hydroxypropylamino, N,N-bis(2-hydroxyethyl)amino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohecadecylamino, cycloeicosanylamino, cyclotetracosanylamino, phenylamino, N-methylphenylamino, benzylamino, dibenzylamino, piperidyl or morpholyl and, particularly preferably, dimethylamino, diethylamino, di-n-propylamino, di-n-buty
• R 11 and R 12 on their own or together with at least one of the other free radicals selected from R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 can form one or several 5- or 6-membered saturated or unsaturated rings, typically pyridine, pyrrole, piperidine, quinoline or benzoquinolizine derivatives.
• Suitable --COR 13 radicals can be those, wherein R 13 has the meaning given above.
• R 13 to be mentioned are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3,-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl,
• --NR 10 COR 13 radicals can be those, wherein R 13 has the meaning given above and R 14 is hydrogen; C 1 -C 18 alkyl, C 3 - to C 24 cycloalkyl, C 1 -C 4 alkylaryl, each of which is unsubstituted or substituted by cyano groups, hydroxyl groups or C 1 -C 4 alkoxycarbonyl groups; C 6 -C 10 aryl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl groups or by C 1 -C 4 alkoxy groups, or a 5- to 7-membered heterocycle, the meaning of the individual radicals, such as alkyl, alkoxy, aryl etc., conforming to the above definitions thereof, including the preferred ranges cited there, for example o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopent
• radicals to be mentioned are: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N-(4-amino)phthalimido.
• --NR 10 COOR 13 radicals can be those, wherein R 13 and R 10 have the meanings cited above. Examples to be mentioned are: --NHCOOCH 3 , --NHCOOC 2 H 5 and --NHCOOC 6 H 5 .
• R 11 R 12 radicals can be those, wherein R 11 , R 12 and R 10 have the meanings given above. Examples of radicals to be mentioned are: ureido, N-methylureido, N-phenylureido or N,N'-2',4'-dimethylphenylureido.
• R 13 radicals can be those, wherein R 13 has the meaning given above. Examples of radicals to be mentioned are: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino.
• R 13 radicals can be those, wherein R 13 has the meaning given above. Examples of radicals to be mentioned are: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl.
• --SOR 13 radicals can be those, wherein R 13 has the meaning given above. Radicals to be mentioned as examples are phenylsulfoxidyl and methylsulfoxidyl.
• R 13 radicals can be those, wherein R 13 has the meaning given above. Examples of R 13 are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.
• radicals can be those, wherein R 12 and R 12 have the meanings cited above.
• radicals to be mentioned are: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperidylcarbamoyl.
• radicals can be those, wherein R 11 and R 12 have the meanings given above. Examples of radicals to be mentioned are: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.
• --N ⁇ NR 15 radicals can be those, wherein R 15 is the radical of a coupling component or a phenyl radical which is unsubstituted or substituted by halogen, alkyl or --O-alkyl, wherein halogen and alkyl have the meanings given above.
• Alkyl in the definitions of R 15 can contain one of the preferred numbers of carbon atoms indicated above. Examples of R 15 to be mentioned are: the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or p-N,N-dimethylaminophenyl radicals.
• --OCOR 13 radicals can be those, wherein R 13 has the meaning cited above. Examples of R 13 to be mentioned are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
• --OCONHR 13 radicals can be those, wherein R 13 has the meaning cited above. Examples of R 13 to be mentioned are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
• X may be C 1 -C 37 alkandiyl, for example methylene, 1,1-, 1,2-ethanediyl, 1,1-, 1,2-, 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,11-undecanediyl, 1,12-dodecanediyl, 1,13-tridecanediyl, 1,14-tetradecanediyl, 1,15-pentadecanediyl, 1,16-hexadecanediyl, 1,17-heptadecanediyl, 1,18-octadecanediyl, 1,19-nonadecaned
• Particularly preferred perylene-3,4:9,10-tetracarboxylic acid imides of the general formula I are those, wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are hydrogen, R 1 is a secondary alkyl radical, such as 1-(C 1 -C 9 alkyl)-C 2 -C 10 alkyl, in particular those, wherein R 1 has a "swallowtail structure", for example 1-methylethyl, 1-ethyl-n-propyl, 1-n-propyl-n-butyl, 1-n-butyl-n-pentyl, 1-n-hexyl-1-heptyl, 1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl, 1-n-nonyl-1-decyl, and also aromatic radicals, preferably phenyl radicals, very particularly preferably C 1 -C
• novel perylene monocarboxylic acids I are preferably obtained by reacting perylene anhydride imides of the general formula III ##STR4## with an amino acid of formula IV
• This invention thus also relates to a process for the preparation of perylene imides, which comprises reacting a perylene anhydride imide with a primary amine at elevated temperature, the perylene anhydride imide III being reacted with an amino acid IV.
• the reaction is preferably carried out at reaction temperatures in the range from 80 to 150, particularly preferably from 100 to 130° C.
• the success of the reaction does not depend on the choice of the pressure range.
• the reaction is usually carried out at atmospheric pressure, but it is also possible to choose lower pressure ranges of up to 10 kPa or of up to 10 Mpa.
• the reaction times are preferably chosen in the range from 30 min to 2.5 h, depending on the chosen reaction temperature.
• the reaction is carried out in the presence of a basic organic solvent, preferably in the presence of a nitrogen-containing heterocycle such as imidazole, quinoline, pyridine, picoline or N-methylpyrrolidone, particularly preferably imidazole or quinoline.
• a basic organic solvent preferably in the presence of a nitrogen-containing heterocycle such as imidazole, quinoline, pyridine, picoline or N-methylpyrrolidone, particularly preferably imidazole or quinoline.
• the reaction can also be carried out using a glycol, such as ethylene glycol or diethylene glycol.
• the amount of base used is usually chosen in the range from 0.1 to 1 mol per 1 kg solvent, preferably 0.1 to 0.5 mol per kg solvent.
• the reaction is carried out in melted imidazole at a temperature in the range from 100 to 130° C.
• the reaction is carried out in a protective gas atmosphere.
• protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
• the amino acid IV is usually used in excess, preferably in a molar ratio of 1.1:1 to 20:1, particularly preferably of 1.3:1 to 15:1 (amino acid IV: perylene anhydride imide III).
• heavy metal salts for example the zinc, lead, calcium, copper, manganese, iron, cobalt, nickel, tin, silver or magnesium salts, such as chlorides, sulfates, nitrates or acetates, preferably water-soluble zinc salts, such as zinc acetate and zinc chloride.
• the molar ratio of perylene anhydride imide III to heavy metal salt is usually chosen in the range from 10:1 to 1:10, preferably from 2.5:1 to 1:2.5.
• Perylene-3,4:9,10-tetracarboxylic acid monoanhydride monoimides of formula III are known or can be prepared by known methods, for example by
• Preferred perylene anhydride imides III are those, wherein R 1 is an aliphatic radical as defined above, preferably a secondary alkyl radical such as 1-(C 1 -C 9 alkyl)-C 2 -C 10 alkyl, R 1 preferably having a "swallowtail structure" which may be realised with radicals such as 1-methylethyl, 1-ethyl-n-propyl, 1-n-propyl-n-butyl, 1-n-butyl-n-pentyl, 1-n-hexyl-1-n-heptyl, 1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl, 1-n-nonyl-1-n-decyl.
• R 1 is an aliphatic radical as defined above, preferably a secondary alkyl radical such as 1-(C 1 -C 9 alkyl)-C 2 -C 10 alkyl
• R 1 preferably having
• Amino acids IV can, in principle, be all known amino acids as long as they do not interfere with the desired reaction. Those amino acids IV are preferred, wherein X is C 1 -C 37 alkanediyl, such as methylene, 1,1-, 1,2-ethanediyl, 1,1-, 1,2-, 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,11-undecanediyl, 1,12-dodecanediyl, 1,13-tridecanediyl, 1,14-tetradecanediyl, 1,15-pentadecanediyl, 1,16-hexadecanediyl, 1,17
• Particularly preferred amino acids IV are 4-aminobenzoic acid, 3-aminobenzoic acid, 2-aminobenzoic acid, the natural amino acids containing a primary amino group, such as glycine, ⁇ -alanine, histidine, leucine, ornithine, phenylalanine, tryptophane or valine, 4-aminobutyric acid, 6-aminocaproic acid and 11-aminoundecanoic acid.
• a primary amino group such as glycine, ⁇ -alanine, histidine, leucine, ornithine, phenylalanine, tryptophane or valine
• 4-aminobutyric acid such as 6-aminocaproic acid and 11-aminoundecanoic acid.
• novel perylene derivates I can be purified and isolated by customary methods, for example by chromatography, preferably column chromatography, or by extractive recrystallisation. The perylene derivatives I can then usually be used directly for further reactions.
• a particularly preferred embodiment of this invention relates to the working up of the reaction mixture, adding prior to the customary purification steps an acid to the reaction mixture, preferably a mineral acid, particularly preferably a semi-concentrated, for example 1.5 to 3N, preferably 2N, mineral acid, or a concentrated mineral acid, for example semi-concentrated, preferably 2N, hydrochloric acid, or concentrated hydrochloric acid.
• an acid to the reaction mixture preferably a mineral acid, particularly preferably a semi-concentrated, for example 1.5 to 3N, preferably 2N, mineral acid, or a concentrated mineral acid, for example semi-concentrated, preferably 2N, hydrochloric acid, or concentrated hydrochloric acid.
• the amount of acid used usually depends on the choice of the substituents and the strength and kind of acid used.
• the acid is usually added in excess amount.
• the amount of acid used is typically in the range from 100 to 1000 I per mol of perylene anhydride imide III used.
• the customary treatment of the crude reaction mixture with an alcohol is preferably avoided, especially if there is no not wish to esterify perylene I.
• novel perylene-3,4-dicarboxylic acid imides II are preferably obtained in analogy to the above-mentioned methods by reacting the corresponding perylene-3,4-dicarboxylic acid anhydrides (known, inter alia, from Liebigs Ann. (1995) p.1229 et seq. or from Liebigs Ann./Recueil (1997) 467 et seq.) with the amino acids IV.
• the reaction conditions and ratios of the educts also correspond to the above conditions.
• another embodiment of this invention relates to a process for the preparation of perylene-3,4-dicarboxylic acid imides II, which comprises reacting a perylene-3,4-dicarboxylic acid anhydride with an amine at elevated temperature, the amine used being the amino acid IV, and the perylene-3,4-dicarboxylic acid anhydride used being the compound of the general formula V ##STR5##
• Preferred perylene-3,4-dicarboxylic acid imides II are those, wherein R 1 to R 16 are the groups defined above as preferred.
• perylene-3,4-dicarboxylic acid imides II are those, wherein R 1 to R 9 and R 16 are hydrogen, and X is a C 1 -C 37 alkanediyl radical.
• 11-[(N-perylene-3,4-dicarboximide)-yl]-undecanoic acid may be mentioned as example.
• Another embodiment of this invention relates to perylene imide carboxylic acid derivatives VI and VII ##STR6##
• R 1 to R 9 and X have the definitions given above, X not being a divalent carbocyclic or heterocyclic aromatic radical, and Y being a radical of an alcohol, of --OR 10 , of an amine, of --NR 11 R 12 or of a halogen, such as chloro or bromo.
• Particularly preferred perylene imide carboxylic acid derivatives VI and VII are those, wherein R 1 to R 9 and R 16 are hydrogen, X is a C 1 -C 37 alkanediyl radical, and R 10 , R 11 and R 12 are hydrogen.
• novel perylene imide carboxylic acid derivatives VI and VII are usually obtained by methods known per se (see, for example, Organikum, p.440 et seq, chap. 7.1.5.1, 9 th edition, 1969) for the preparation of carboxylates and carboxylic acid amides, so that further details may be dispensed with here.
• the novel perylene imide monocarboxylic acids I and the perylene-3,4-dicarboxylic acid imides II may thus by esterified by acid catalysis.
• Suitable catalysts are the standard known catalysts such as sulfuric acid, hydrogen chloride, toluenesulfonic acid, naphthalenesulfonic acid or hydrogen-charged acid ion exchangers.
• Reactions of this kind i.e. the esterification or formation of carboxylic acid amides, are generally interesting e.g. for the use of the novel perylenecarboxylic acids I or II as fluorescent markers.
• novel perylene imide carboxylic acids I or II are suitable, inter alia, preferably for modifying inorganic substrates such as aluminium oxide, silicium dioxide, titanium dioxide, tin oxide or silicates or clay minerals since the free carboxyl function is able to ensure adhesion to the surface.
• Another embodiment of this invention relates to the use of the novel perylenes I, II, VI and VII or of their metal ion complexes as colourants, preferably as pigments and dyes, in general by methods known per se, preferably
• polymers for mass colouring polymers
• the polymers can be polyvinyl chloride, cellulose acetate, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones, polyesters, polyethers, polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polybutadiene, polychlorobutadiene or polyisoprene, or the copolymers of the cited monomers;
• vat dyes or mordant dyes for example for dyeing natural substances and, in particular, paper, wood, straw, leather, hides or natural fibre materials, such as cotton, wool, silk, jute, sisal, hemp, flax or animal hair (e.g. horsehair) and the conversion products thereof, such as viscose fibre, nitrate silk or cuprammonium rayon (rayon), preferred salts for mordanting being aluminium salts, chromium salts and iron salts;
• colourants such as pigments and dyes, where a specific colour shade is to be achieved, particularly luminous shades being preferred
• novel colourants for tracer purposes, e.g. in biochemistry, medicine, technology and natural science, where the novel colourants can be linked covalently to the substrates or via secondary valences, such as hydrogen bonds or hydrophobic interactions (adsorption);
• inorganic substrates such as aluminium oxide, silicium oxide, titanium dioxide, tin oxide, magnesium oxide (especially "stone wood"), silicates, clay minerals, calcium-, gypsum- or cement-containing surfaces, for example coatings or plaster surfaces, where the free carboxyl function ensures special surface adhesion.
• the crude product is worked up by chromatography over silica gel/chloroform/glacial acetic acid (10+1).
• the colourant is suspended in ethyl acetate and applied to a chromatographic column (silica gel/ethyl acetate), including the substrates.
• a chromatographic column sica gel/ethyl acetate
• the mobile phase is changed (chloroform/glacial acetic acid (10+1)).
• the product dissolves completely and starts to move on the column as a wide band.
• the combined phases of the main run which are thin-layer chromatographically uniform, are freed from the eluant mixture and taken up in a small amount of chloroform and filtered through a D4 frit.
• the filtrate is transferred to a round-bottom flask, covered with a large amount of distilled water, and the chloroform is then drawn off.
• the precipitated colourant is separated via a frit and dried at 100° C.
• the precipitate stores the water especially.
• the product is therefore transferred to an agate mortar and the colourant is carefully ground, upon which the water bound in the precipitate is released.
• the precipitate is then dried and the procedure is repeated until the pure product can be powdered and dried for 24 h at 80° C. in an oil pump vacuum.
• the chloroform phase is applied to a chromatographic column (aluminium oxide/chloroform), the product remaining firmly adsorbed on the aluminium oxide while at least two impurities can be eluted.
• the colourant can be desorbed by adding 10 vol.-% of glacial acetic acid to the eluant.
• the colourant is chromatographed once more over silica gel/chloroform/glacial acetic acid (10+1).
• the combined phases of the main run which are thin-layer chromatographically uniform, are freed from the eluant mixture and are taken up in a small amount of chloroform and filtered through a D4 frit.
• the filtrate is transferred to a round-bottom flask and covered with a large amount of distilled water, and the chloroform is then drawn off.
• the precipitated colourant is separated via a frit and dried at 100° C.
• IR (KBr): n 2950 cm -1 (m), 2926 (s), 2854 (m), 1715 (s), 1699 (s), 1660 (s br.), 1594 (s), 1579 (m), 1505 (w), 1490 (w), 1456 (m), 1435 (m), 1405 (s), 1370 (m sh), 1351 (s sh), 1345 (s), 1300 (w), 1256 (m), 1202 (w), 1178 (w), 1140 (w), 1125 (w), 1075 (w), 960 (w), 851 (m), 810 (s), 794 (w), 747 (m), 648 (w), 635 w.
• IR (KBr): n 2955 cm -1 (m), 2929 (m), 2857 (m), 1735 (w br.), 1700 (s), 1660 (s), 1616 (w), 1595 (s), 1579 (m), 1507 (w), 1457 (w), 1437 (m), 1404 (m), 1378 (w), 1346 (s br.), 1304 (w), 1253 (m), 1195 (w), 1173 (m), 1129 (w), 993 (w), 855 (w), 810 (s), 749 (m), 623 (w).
• UV (CHCl 3 ): I max (e) 526 nm (79000), 490 (47300), 458 (16900).
• the crude product is chromatographed twice over silica gel using chloroform/glacial acetic acid (10+1) as eluant, it being possible to separate several by-products with the forerun.
• the further purification of the colourant is carried out by extractive recrystallisation from chloroform. After the extraction is complete, the chloroform phase is covered with pentane and the closed flask is left standing for several days.
• the organic phase is filtered over aluminium oxide (column 10 ⁇ 4 cm) with addition of 10 vol.-% glacial acetic acid.
• the crude product is chromatographed over silica gel (column 50 ⁇ 4 cm)/chloroform/glacial acetic acid (10+1) and a nonuniform orange-red forerun can be separated.
• the combined phases of the main run which are thin-layer chromatographically uniform, are freed from the eluant mixture, taken up in a small amount of chloroform and filtered through a D4 frit.
• the filtrate is transferred to a round-bottom flask, covered with a large amount of distilled water, and the chloroform is then carefully drawn off.
• the precipitated colourant is then separated via a frit and dried at 100° C.
• IR (KBr): n 2955 cm -1 (m), 2928 (m), 2857 (m), 1730 (w sh), 1696 (s br.), 1658 (s), 1616 (w), 1595 (s), 1579 (m), 1506 (w), 1457 (w), 1439 (m), 1405 (s), 1385 (w), 1355 (m), 1342 (s), 1253 (m), 1217 (w), 1176 (w), 1126 (w), 905 (w), 855 (w), 810 (s), 747 (m), 668 (w).
• UV (CHCl 3 ): I max (e) 526 nm (80800), 489 (48400), 458 (17700).
• IR (KBr): n 2953 cm -1 (m), 2926 (s), 285 (m), 1728 (m sh), 1697 (s), 1658 (s), 1615 (w), 1595 (s), 1579 (m), 1508 (w), 1458 (m), 1439 (m), 1405 (s), 1389 (w), 1355 (m sh), 1342 (s), 1254 (m), 1217 (w), 1176 (m), 1126 (w), 1108 (w), 1092 (w), 853 (m), 810 (s), 796 (w), 746 (m), 655 (w).
• any remaining fluorescent impurity is separated over silica gel/chloroform /ethanol (10+1).
• the combined phases of the main run which are thin-layer chromatographically uniform, are freed from the eluant mixture and taken up in a small amount of chloroform/glacial acetic acid and filtered through a D4 frit.
• the filtrate is transferred to a round-bottom flask, covered with a large amount of distilled water, and the chloroform is then drawn off.
• the precipitated colourant is then separated via a frit and dried at 100° C.
• the pure product is powdered in an agate mortar and dried for 24 h at 80° C. in an oil pump vacuum. Yield: 110 mg (59%), m.p.
• the main product with the highest R f -value can be roughly separated from the other six by-products by column chromatography (silica gel/chloroform/ethanol (10+1)).
• the ultrapurification is carried out over aluminium oxide (column 40 ⁇ 4 cm) using chloroform as eluant, the product moving very slowly. The remaining impurities, however, remain firmly adsorbed to the column material.
• IR (KBr): n 2956 cm -1 (m), 2928 (m), 2858 (m), 1 724 (m), 1697 (s), 1658 (s), 1596 (s), 1578 (m), 1508 (w), 1458 (w), 1438 (m), 1404 (m), 1343 (s), 1253 (m), 1178 (m), 1126 (w), 1109 (w), 1084 (w), 1032 (w), 853 (w), 810 (m), 796 (w), 747 (m).

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• 1998
  • 1998-12-03 US US09/204,189 patent/US6166210A/en not_active Expired - Fee Related
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